CN105254847B - Varnish, prepreg, the film containing resin, the plywood of coated metal foil, printed wiring board - Google Patents

Varnish, prepreg, the film containing resin, the plywood of coated metal foil, printed wiring board Download PDF

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Publication number
CN105254847B
CN105254847B CN201510802437.1A CN201510802437A CN105254847B CN 105254847 B CN105254847 B CN 105254847B CN 201510802437 A CN201510802437 A CN 201510802437A CN 105254847 B CN105254847 B CN 105254847B
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China
Prior art keywords
varnish
resin
amino
formula
compound
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CN201510802437.1A
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CN105254847A (en
Inventor
森田高示
村井曜
高根泽伸
井上康雄
坂井和永
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Lishennoco Co ltd
Resonac Holdings Corp
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Hitachi Chemical Co Ltd
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Priority claimed from JP2010039388A external-priority patent/JP5136573B2/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/508—Amines heterocyclic containing only nitrogen as a heteroatom having three nitrogen atoms in the ring
    • C08G59/5086—Triazines; Melamines; Guanamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/246—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using polymer based synthetic fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/04—Epoxynovolacs
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B32B2262/0269—Aromatic polyamide fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48225—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H01L2224/48227—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73265—Layer and wire connectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/73—Means for bonding being of different types provided for in two or more of groups H01L24/10, H01L24/18, H01L24/26, H01L24/34, H01L24/42, H01L24/50, H01L24/63, H01L24/71
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/153—Connection portion
    • H01L2924/1531—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface
    • H01L2924/15311—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface being a ball array, e.g. BGA
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics

Abstract

The present invention provides a kind of varnish, be make in a solvent containing polycycle structure and have the resin of functional group reacted with amino the functional group at least part, reacted with the amino of the compound with amino prepared by；The present invention provides a kind of varnish, be make in a solvent containing polycycle structure and have the resin of functional group reacted with phenolic hydroxyl group the functional group at least part, reacted with the phenolic hydroxyl group of the compound with phenolic hydroxyl group prepared by.In addition, the present invention provides the plywood and printed wiring board for using prepreg prepared by any varnish among the above, the film containing resin, coated metal foil.

Description

Varnish, prepreg, the film containing resin, the plywood of coated metal foil, printing electricity Road wiring plate
The application is divisional application, the application number of parent application: 201080064778.9, the applying date: and 2010.8.13, Denomination of invention: varnish, prepreg, the film containing resin, the plywood of coated metal foil, printed wiring board
Technical field
The present invention relates to varnish used in plywood and printed wiring board etc. for e-machine of production, And use prepreg, the film containing resin, the plywood of coated metal foil, printed circuit wiring obtained by varnish production Plate.
Background technique
In recent years, carrying out miniaturization, the lighting of e-machine always, and for the printing of e-machine electricity Road circuit board needs the high-density wiring realized based on slim multiple stratification or fine wiring etc..In order to realize high density cloth Line, printed wiring board are needed for the purpose of the reliability for improving the fine wiring on substrate by low thermal expansion rate. Especially used in semiconductor chip etc. as the package substrate for the high-density printed circuit circuit board for being equipped with semiconductor equipment On the way, required characteristic is tightened up compared with core substrate etc..
In addition, flip-chip connection type is widely used to replace previous wire bonding mode as installation method.? Load connection type is by soldered ball come the lead in the way of replacing for wire bonding, thus to wiring plate and semiconductor equipment into The method of row connection, installation.As the semiconductor packages for using the installation method, CSP (chip size packages (chip can be enumerated Scale package)), PoP (stacked package (Package on Package)) and SiP (system in package (System in Package)) etc..
In the case where being attached by means of the soldered ball, in Reflow Soldering, soldered ball and wiring plate are heated to about 300 ℃.The wiring plate usually film by prepreg or containing resin and the plywood for being laminated with metal foil are constituted, the prepreg It is made of resin combination and fiber base material or supporting mass, and makes to form wiring using metal foil.Therefore, wiring plate is because of warm And expand, due to the difference of mounted electronic component (especially semiconductor equipment) and the coefficient of thermal expansion of the resin of wiring plate And lead to the deformation of the referred to as substrate of warpage, especially sent out in the soldered ball of interconnecting piece for being located at semiconductor equipment and wiring plate Raw stress is concentrated, there are generation crack, the problem of causing bad connection.
For the warpage of the semiconductor packages of PoP structure, specifically described using Fig. 1.Firstly, semiconductor packages Semiconductor core made of the electrical connection of bonding wire 14 is utilized by carrying on the conductor package substrate 16 for be formed with soldered ball 22 Piece 10 forms, wiring plate obtained by the setting of soldered ball 22 on substrate 18 is sealed using sealant 12 on it.At this Under state, if being heated to wiring plate, because of the difference of sealing material 12 and the coefficient of thermal expansion of chip 10 and conductor package substrate 16 And warpage occurs, generate crack C.
Using this situation as background, need to be not likely to produce the plywood of warpage and low thermal expansion rate.As previous stacking Plate is usually overlapped more pieces of prepregs, and metal foil is further arranged on single or double and carries out heating pressurization and is made , the prepreg is to make to contain with the resin combination of epoxy resin host agent to be immersed in glass woven fabric or non-woven fabrics and carry out Obtained by drying.The balance of insulating properties, heat resistance, the cost of epoxy resin etc. is excellent, but coefficient of thermal expansion is big.Therefore, example Such as, as disclosed in Patent Document 1, the inorganic filling materials such as silica are added usually to keep the heat of resin combination swollen Swollen rate reduces.
By highly-filled inorganic filling material, so as to further decrease coefficient of thermal expansion.But from by inorganic fill Moisture absorption caused by material, the reduction of insulating reliability, the deterioration of resin-wiring layer poor attachment and drill processability From the aspect of, multiwiring board, package substrate are the presence of limitation with highly-filledization on the way.
The crosslink density of resin combination is improved, high Tgization is realized, reduces thermal expansion in addition, patent document 2 and 3 discloses The method of rate.But improving crosslink density is by realizing the strand between crosslinking and shortening, in reactivity, resin There is limitation in the aspect of structure.
On the other hand, as the effective ways for reducing coefficient of thermal expansion, patent document 4 is disclosed between making crosslinking points at molecular weight In proper range, method using the epoxy resin with polycycle structure.But the previous ring with polycycle structure Oxygen resin due to polycycle structure division attracting each other for molecular separating force and crystallize, dissolubility in a solvent is low, because And even if being made it dissolve in organic solvent by heating, if being back to room temperature can also recrystallize.
In turn, as the effective method for realizing low warpage properties, patent document 5 is disclosed using containing polycycle structure The method of resin.It is this effective master on the way that patent document 5, which describes the resin containing polycycle structure in sealing material use, Purport.In the case where sealant use, it is not necessary to carry out varnish, not the knot again in the case where dissolving in organic solvent Brilliant problem.
But in the case where being unfolded to study to plywood purposes, as described above, the resin containing polycycle structure is having Unusual indissoluble in solvent, and exist by storage stability difference such problems under the room temperature in the state of varnish, Need to dissolve progress varnish in a solvent before the manufacture that will carry out plywood.
Therefore, as long as the storage stability of the resin containing polycycle structure at normal temperature can be improved, so that it may improve and use Operability when varnish is industrially significantly.
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2004-182851 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2000-243864 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2000-114727 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2007-314782 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2007-002110 bulletin
Summary of the invention
Excellent clear of operability high the purpose of the present invention is to provide storage stability at normal temperature and when in use Paint, and use the plywood and printed circuit wiring of prepreg made of the varnish, the film containing resin, coated metal foil Plate.
It conducts in-depth research to achieve the above object, as a result the present inventor contemplates following present invention.The present invention is such as It is lower described.
[1] a kind of varnish is the tree for making containing polycycle structure and having the functional group reacted with amino in a solvent A part of the above-mentioned functional group of rouge, reacted with the amino of the compound with amino prepared by.
[2] varnish according to [1] is to make in above-mentioned solvent containing polycycle structure and have and phenolic hydroxyl group A part of the above-mentioned functional group of the resin of the functional group of reaction, with the phenolic hydroxyl group of the compound with phenolic hydroxyl group into Prepared by row reaction.
[3] varnish according to [1] or [2], wherein the above-mentioned compound with amino is guanamines, dicyandiamide and ammonia Any compound in base triazine novolac resin.
[4] a kind of varnish is to make in a solvent containing polycycle structure and have the functional group reacted with phenolic hydroxyl group Resin above-mentioned functional group a part, reacted and be made with the phenolic hydroxyl group of the compound with phenolic hydroxyl group 's.
[5] varnish according to [2] or [4], wherein the above-mentioned compound with phenolic hydroxyl group is phenol novolacs Resin or cresol novolac resin.
[6] varnish according to any one of [1]~[5], which is characterized in that above-mentioned resin at least contains 1 conduct The epoxy group of above-mentioned functional group.
[7] varnish according to any one of [1]~[6], wherein above-mentioned resin, which has, is selected from biphenyl structural, naphthalene knot At least one of structure, biphenyl novolaks resin structure, anthracene structure, dihydroanthracene structure structure.
[8] a kind of varnish contains the resin component of the structure indicated with following formula (1).
(in above-mentioned formula, R1For the residue of the compound with amino.)
[9] varnish according to [8], relative to above formula (1) indicate structure and following formula (2) indicate structure it is respective The summation there are ratio for, above formula (1) indicate structure there are ratio be 40% or less.
[10] a kind of prepreg is that varnish described in any one of [1]~[9] is coated on substrate and is added Heated drying and it is manufactured.
[11] prepreg according to [10], wherein above-mentioned substrate is glass woven fabric, glass non-woven fabric, aromatics are poly- Amide woven fabric or aramid nonwoven fabric.
[12] a kind of film containing resin is that varnish described in any one of [1]~[9] is coated on film and is carried out Heat drying and it is manufactured.
[13] a kind of plywood of coated metal foil, at least one mask of the prepreg described in [10] or [11] There is conductor layer.
[14] a kind of plywood of coated metal foil, at least one face of the film containing resin described in [12] have Conductor layer.
[15] a kind of printed wiring board, be to the plywood of the coated metal foil described in [13] or [14] extremely Prepared by the formation that above-mentioned conductor layer possessed by a few face is routed.
Using the present invention, it is capable of providing operational excellent varnish when storage stability height and use at normal temperature, And manufactured prepreg, the film containing resin, the plywood of coated metal foil and printed circuit cloth using the varnish Line plate.
Detailed description of the invention
Fig. 1 is the explanatory diagram for indicating the warped state of semiconductor packages of PoP structure.
Fig. 2 is DSC curve obtained by being measured with equivalent proportion 1:1 to YX-8800 and dicyandiamide.
Specific embodiment
[1] varnish:
First varnish of the invention is to make in a solvent containing polycycle structure and have the functional group reacted with amino At least part of the functional group of resin, reacted with the amino of the compound with amino prepared by.
First varnish of the invention also may be referred to the resin component containing the structure indicated in structure with following formula (1) Varnish.
In above-mentioned formula, R1It is the residue with the compound of amino.For the compound with amino, followed by chatting It states.
In addition, the second varnish of the invention is to make to react containing polycycle structure and having with phenolic hydroxyl group in a solvent At least part of the functional group of the resin of functional group is reacted with the phenolic hydroxyl group of the compound with phenolic hydroxyl group Prepared by.For the compound with phenolic hydroxyl group, followed by narration.
It should be noted that in the present specification, " the tree containing polycycle structure and with the functional group reacted with amino Rouge " and " resin containing polycycle structure and with the functional group reacted with phenolic hydroxyl group " are suitble to be referred to as " containing polycycle knot The resin of structure ".
(by these varnish, together simply referred to as " of the invention is clear sometimes below for first varnish of the invention and the second varnish Paint ") be by will the resin containing polycycle structure and the compound with amino or the compound with phenolic hydroxyl group dispersion In a solvent, then carrying out heating etc. carries out reaction, can be improved the molten of the resin containing polycycle structure prepared by Agent dissolubility and the varnish that can be realized long-term preservation.Additionally, it is not necessary to containing for improving deliquescent additive, therefore, tree The reduction of the characteristic of rouge is less and characteristic remains excellent.
Hereinafter, varnish of the invention is described in detail.
(resin containing polycycle structure)
" the polycycle structure " of resin of the present invention containing polycycle structure refers to aromatic rings each other by singly-bound Structure obtained by key structure with obtained by or aromatic rings are condensed.
As aromatic rings each other by singly-bound key structure with obtained by, such as biphenyl structural, biphenyl novolaks can be enumerated Resin structure, terphenyl structure etc..
In addition, as aromatic rings through structure obtained by condensed, for example, can enumerate naphthalene structure, naphthol novolak varnish gum structure, The luxuriant and rich with fragrance structure of anthracene structure, dihydroanthracene structure, luxuriant and rich with fragrance structure, aphthacene structure, structure, benzo [9,10], benzanthracene structure, pyrene structure, Pi structure and structure etc..
Above-mentioned such structure can be used alone any structure therein, two or more can also be applied in combination.From making The characteristic (thermal expansivity, heat resistance etc.) of the plywood made of varnish of the invention, printed wiring board, installation base plate etc. Aspect is set out, preferably biphenyl structural, biphenyl novolaks resin structure, naphthalene structure, naphthol novolak varnish gum structure, anthracene structure With dihydroanthracene structure etc., more preferably biphenyl structural, biphenyl novolaks resin structure, naphthalene structure, anthracene structure, dihydroanthracene knot Structure.This is because have because stereochemical structure is fixed and can easily generate the feature banked up, it is advantageous to.
Resin containing polycycle structure mobility when heated is high, therefore, from after solidification heat resistance and size it is steady Qualitatively aspect is set out, preferably heat-curing resin.As heat-curing resin, epoxy resin, cyanate ester resin can be enumerated Deng, but from productivity and operational aspect, preferably epoxy resin.
It should be noted that for epoxy resin, the functional group reacted with amino and reacted with phenolic hydroxyl group Functional group be epoxy group.
In above-mentioned epoxy resin, from mouldability aspect, preferably naphthol novolak type epoxy resin, biphenyl phenolic aldehyde Type epoxy resin, from low heat expansion aspect, preferably naphthalene type epoxy resin, anthracene type epoxy resin, dihydroanthracene type Epoxy resin.These epoxy resin can be used alone or two or more is applied in combination.But in order to play their performance, phase For epoxy resin total amount, preferably amounts to and use their 30 mass % or more, more preferably use 50 mass % or more.
Hereinafter, showing the concrete example of preferred epoxy resin.
As biphenyl phenolic resin varnish type epoxy resin, the preferably epoxy resin of following formula (3) expression.As with formula (3) table The epoxy resin for the structure shown, such as NC-3000 (Nippon Kayaku K. K's system) can be obtained in the form of commercially available product.
In above-mentioned formula, R4~R7It is identical or different, indicate hydrogen or alkyl.In addition, n is the number for indicating n > 0, preferably 1.5 ≤n≤4.0。
As naphthol novolak type epoxy resin, the epoxy resin of the structure preferably indicated with following formula (4).As having The epoxy resin for the structure that formula (4) indicates, such as the form of commercially available product obtain ESN-175 (Toto Kasei KK System).
M in above-mentioned formula is the number for meeting m > 0, preferably 2≤m≤7.
As dihydro anthracene type epoxy resin, it is however preferred to have the epoxy resin for the structure that following formula (5) indicates.As with formula (5) epoxy resin of the structure indicated, such as the form of commercially available product obtain YX-8800 (Japanese epoxy resin Co., Ltd. System).
In above-mentioned formula, R8And R9It is identical or different, and indicate the alkyl below of carbon number 4.X indicates that 0~4 integer, y indicate 0 ~6 integer.)
As anthracene type epoxy resin, the epoxy resin of the structure preferably indicated with following formula (6).
In formula, R14~R17With the R in formula (3)4~R7It is identical.
(compound with amino)
As long as the compound of the present invention with amino has at least more than one amino, example in the molecule It such as, will " reactive group of the compound with amino round and round equivalent ": " epoxide equivalent with the epoxy resin of polycycle structure " Beginning heating temperature when being set as 1:1 is preferably 60 DEG C or more 200 DEG C or less, and further preferably 70 DEG C or more 190 DEG C Hereinafter, particularly preferably 80 DEG C or more 180 DEG C or less.If in the range of the beginning heating temperature, consolidating at normal temperature Changing reaction would not hastily carry out, and therefore, storage stability (storage stability) can be improved.
Start heating temperature measurement can be measured by DSC (Differential scanning calorimetry) into Row metering.Specifically, can in Fig. 2 (DSC curve obtained by being measured with equivalent proportion 1:1 to YX-8800 and dicyandiamide), It is found out by the upward inflection point (the point A of Fig. 2) of curve.
As the compound with amino, such as the guanamines such as benzoguanamine, acetylguanamine system, spiral shell guanamines can be enumerated or by it It is derivative obtained by guanamine resin, dicyandiamide, melamine or available melamine resin, triethylene four are derived by it Amine, amino triazine novolac resin etc..The molecular weight of these compounds is preferably 60 or more, and further preferably 80 or more. By being at such molecular weight, to be reacted in the compound with amino with the resin containing polycycle structure And key occurs in the case where, it can fully prevent the resin containing polycycle structure from orientation occurs and is crystallized.In addition, also Several compounds with amino can be used together.Wherein, from the side such as plywood thermal expansivity after molding, heat resistance, reliability Face is set out, preferably benzoguanamine, dicyandiamide, amino triazine novolac resin.
In addition, as the R in formula (1)1That is the residue of the compound with amino, can enumerate foregoing illustrative resin or change Close the residue of object.
(compound with phenolic hydroxyl group)
As long as the compound with phenolic hydroxyl group being used in the present invention has 1 or more hydroxyl in the molecule, From crosslinking aspect, further preferably there are 2 or more hydroxyls.Such as naphthalene glycol, phenol resol resins, first can be enumerated Phenol novolac resin, bisphenol A-type novolac resin, amino triazine novolac resin, the amino containing bismaleimide Triazine novolac resin, bisphenol-A, Bisphenol F etc..Wherein, preferably phenol resol resins, cresol novolac resin. The molecular weight of these compounds is not particularly limited, can also and with several.
Here, by " the reactive group equivalent of the compound with phenolic hydroxyl group ": " epoxy resin with polycycle structure Epoxide equivalent " beginning heating temperature when being set as 1:1 is 60 DEG C or more 200 DEG C or less, further preferably 70 DEG C with Upper 190 DEG C hereinafter, particularly preferably 80 DEG C or more 180 DEG C or less.If in the range of the beginning heating temperature, room temperature Under curing reaction would not hastily carry out, therefore, storage stability (storage stability) can be improved.
It should be noted that using the compound with phenolic hydroxyl group, and with aftermentioned curing accelerator.
In addition, can be used in combination with the compound with amino in the reaction of the compound with phenolic hydroxyl group in a solvent.? In this case, for 1 equivalent of compound with amino, the compound with phenolic hydroxyl group is preferably made to reach 0.01 ~100 equivalents, more preferably up to 0.03~30 equivalent.By reaching 0.05~20 equivalent, so as to efficiently make with phenol Compound, the compound with amino and the heat-curing resin of property hydroxyl are reacted.
Here, by " the reactive group equivalent of the compound with phenolic hydroxyl group and the compound with amino ": " having more Beginning heating temperature when the epoxide equivalent of the epoxy resin of ring structures " is set as 1:1 be preferably 60 DEG C or more 200 DEG C or less i.e. Can, further preferably 70 DEG C or more 190 DEG C hereinafter, particularly preferably 80 DEG C or more 180 DEG C or less.As long as being in the beginning In the range of heating temperature, the curing reaction under room temperature would not be carried out hastily, therefore, storage stability can be improved and (save Stability).
(resin component with the structure that formula (1) indicates)
The resin component of the structure of the present invention indicated with formula (1) can be above-mentioned with polycyclic by making in a solvent The epoxy resin of formula structure is reacted with the compound with amino and is made.Specifically, can be by making epoxy resin At least part of epoxy group is reacted with the amino of the compound with amino, and obtains the structure that there is formula (1) to indicate Resin component.
The example for the structure that formula (1) of the invention indicates is as follows.
Firstly, being set using made from the biphenyl phenolic resin varnish type epoxy resin of formula (3) expression and the compound with amino The structure that there are rouge ingredient following formula (7) to indicate.
In above-mentioned formula, R1It is identical as formula (1) (same as below).O is the number for meeting o > 0, and p is the number for meeting p > 0.
In addition, utilizing resin made from the naphthol novolak type epoxy resin of formula (4) expression and the compound with amino The structure that there are ingredient following formula (8) to indicate.
In above-mentioned formula, q is the number for meeting q > 0, and r is the number for meeting r > 0.
Resin component made from the dihydro anthracene type epoxy resin indicated using formula (5) and the compound with amino includes tool The resin for the structure for thering are following formula (9) to indicate.
In above-mentioned formula, R8And R9, R in x and y and formula (5)8And R9, x and y it is identical.
For varnish of the invention, the respective of structure that the structure and following formula (2) indicated relative to formula (1) indicates is deposited For the summation of ratio, the resin component of above formula (1) expression is 40% hereinafter, more preferably 5% or more there are ratio 40% or less.Moreover, further preferably 8% or more 40% hereinafter, particularly preferably 10% or more 35% or less.
By being in 40% hereinafter, to prevent by the compound with amino of modified addition with polycycle The molecule of the epoxy resin of structure is aligned and is crystallized, and therefore, will not be recrystallized, and can be obtained saving and be stablized The good varnish of property.
It should be noted that if then leading to the insufficient possibility of storage stability in the presence of curing reaction is promoted more than 40% Property.
In the present invention, to the epoxy resin with polycycle structure, with the compound with amino and/or with phenol For ratio when the reaction of the compound of hydroxyl, relative to the epoxide equivalent of epoxy resin, the ammonia of the compound with amino The range of base equivalent and/or the hydroxyl equivalent of phenolic hydroxyl group preferably from 0.05 to 20, the more preferably range from 0.10 to 10, Particularly preferably from 0.20 to 5.As long as the epoxide equivalent relative to epoxy resin is in 0.05~20, with polycycle structure The solute effect of epoxy resin would not lack and operability is good.In addition, by above range and formula (1) and formula (2) there are ratios to be in already described range, so as to shorten generated time, improve storage stability.
In turn, varnish of the invention contains the structure of following formula (10) in resin component.
In the case where the structure indicated containing above formula (10), the structure that is indicated relative to the formula (1) in resin component For the summation there are ratio for the structure of the structure indicated there are ratio, formula (2) indicated there are ratio and formula (10), formula (1) and the structure that indicates of formula (10) there are the summation of ratio is preferably 40% hereinafter, more preferably 1% or more 40% or less. Moreover, further preferably 5% or more 35% hereinafter, particularly preferred 10% or more 30% or less.
By be in 40% hereinafter, to by means of it is modified carry out addition, the compound with amino can prevent The molecule of epoxy resin with polycycle structure is aligned and is crystallized, and will not be recrystallized, and can be protected Deposit the varnish having good stability.
It should be noted that if then leading to the insufficient possibility of storage stability in the presence of curing reaction is promoted more than 40% Property.
In addition, by by epoxy group: the equivalent proportion of the reactive group of curing agent is adjusted to 0.8~1.2, and varnish is made, To which the characteristic after solidifying can be improved.
In order to have the epoxy resin of polycycle structure with the compound with amino and/or with the change of phenolic hydroxyl group Object mixing is closed, solvent is preferably added to.
As long as solvent, which is free of, makes to have the epoxy resin of polycycle structure and the compound with amino and with phenol hydroxyl Solvent that the compound of base is reacted and being capable of dissolving resin composition, so that it may be arbitrary solvent, particularly preferably acetone, Methyl ethyl ketone, methyl butyl ketone, toluene, dimethylbenzene, ethyl acetate, n,N-Dimethylformamide, N, N- dimethylacetamide The excellent solvent of the dissolubilities such as amine, ethyl alcohol, glycol monoethyl ether, propylene glycol methyl ether acetate.From can dissolving crystallized property it is high Resin in terms of set out, especially preferably propylene glycol monomethyl ether.
As long as the use level of these solvents is without the chemical combination for making to have the epoxy resin of polycycle structure with have amino Solvent that object and compound with phenolic hydroxyl group are reacted and the amount for capableing of dissolving resin composition, so that it may be any Amount, but relative to make to have the epoxy resin of polycycle structure with the compound with amino and with the chemical combination of phenolic hydroxyl group For 100 mass parts of total amount for the resin component that object is reacted, the preferably range of 5~300 mass parts, more preferably 30~ The range of 200 mass parts.In addition, use can also be combined in above-mentioned solvent.
The weight average molecular weight of resin component after reaction of the present invention is preferably 800 or more 4000 hereinafter, more preferably For 900 or more 3500 hereinafter, further preferably 950 or more~3000 or less.The weight average molecular weight example of compound in varnish It can be such as measured by GPC (measurement of calibration curve based on gel permeation chromatography, using standard polystyren).It is logical Crossing makes the weight average molecular weight of the compound in varnish be in above range, is precipitated and improves so that crystallization not occurred Deliquescent, the good varnish of operability of resin containing polycycle structure.
Varnish of the invention can contain resin, curing agent in mentioned component as needed.As long as curing agent has thermosetting The solidification of the property changed resin, there is no particular limitation, as an example, the acid such as maleic anhydride, copolymer-maleic anhydride can be enumerated Acid anhydride, phenolic compounds such as phenol resol resins, cresol novolac resin, amino triazine novolac resin etc..Solidification Agent can be used alone any or two or more be applied in combination.
For varnish of the invention, curing accelerator can be contained when manufacturing plywood.As curing accelerator Example can enumerate imidazoles and its derivative, tertiary amines and quaternary ammonium salt etc..
In turn, in varnish of the invention, in a range that does not hinder the effect of the present invention, it can according to need and cooperate it His ingredient.
As other ingredients, such as the nitrogenous phosphorus compound of organic phosphorus flame retardant, organic system, nitrification can be enumerated The fire retardants such as object, silicone flame retardant, metal hydroxides, the organic filler materials such as Si powder, nylon powder, fluorine powder, The thickeners such as bentonite, modified alta-mud, silicon systems, fluorine system, macromolecular defoaming agent or leveling agent, imidazoles system, thiazole system, three The adaptations imparting agent such as azoles system, silane series coupling agent, the ultraviolet absorbing agents such as enumerate BTA system, hindered phenolic or SP styrenated phenol Equal antioxidants, the Photoepolymerizationinitiater initiaters such as benzophenone, benzyl ketals class, thioxanthones system, the fluorescent whitening agents such as stilbene derivative, Colorants such as phthalocyanine blue, phthalocyanine green, iodine is green, dual-azo yellow, carbon black etc..
In addition, in order to assign low thermal expansion rate, anti-flammability, in a range that does not hinder the effect of the present invention, Ke Yitian Add inorganic filling material, additive.As inorganic filling material, can be used silica, aluminium oxide, aluminium hydroxide, calcium carbonate, Clay, talcum, silicon nitride, boron nitride, titanium oxide, barium titanate, lead titanates, strontium titanates etc..As this use level, relative to this Invention not solvent-laden resin component 100 mass parts of total amount, be set as 300 below the mass, be preferably set to 200 mass parts with Under, this is because can make multiwiring board of the invention with material uniformly and obtain it is good operability and it is preferred that.
Especially using the resin of the present invention containing polycycle structure, inorganic filling material can shape At " nuclei of crystallization " for promoting crystallization, therefore, needed to pay attention in the case where cooperating in large quantities.As additive, can be used each Kind silane coupling agent, curing accelerator, defoaming agent etc..Total amount as its use level, relative to not solvent-laden resin component 100 mass parts, preferably 5 below the mass, from the characteristic aspect for maintaining resin combination, is more preferably set as 3 mass Part or less.It the use of mixing and kneading machine, homogenizer etc. is effective to be uniformly dispersed inorganic filling material.
Resin of the present invention containing polycycle structure is with the compound with amino and/or with phenolic hydroxyl group The reaction of compound is preferably carried out at 80 DEG C or more 250 DEG C or less, is more preferably carried out at 85 DEG C or more 245 DEG C or less, further It is preferred that being carried out at 90 DEG C or more 240 DEG C or less.
In addition, the reaction time preferably carried out at 30 hours 10 minutes or more or less, more preferably at 20 hours 30 minutes or more It carries out, carries out below within further preferably 15 hours 1 hour or more or less.
By being reacted in above-mentioned range, the presence for the resin component that the formula (1) in varnish indicates can be adjusted The structure that the resin component and formula (9) that ratio and formula (1) indicate indicate there are ratios.
Varnish of the invention can form organic insulator in the manufacture of multilayer printed wiring board and package substrate, because This it is preferable to use.Varnish of the invention can also be coated on circuit substrate to form insulating layer, thus industrially preferably Be subject in the form of the sheets stacking material such as adhesive film, prepreg using.
[2] prepreg, the film containing resin, the plywood of coated metal foil, printed wiring board:
Film containing resin of the invention is to be made by varnish coating (brushing) of the invention on supporting mass film by dry Solvent in varnish volatilizees and carries out semi-solid preparation (B-stage), to form film obtained by resin composition layer.In addition, setting Protective film appropriate can be set on oil/fat composition layer.
It should be noted that the state of semi-solid preparation is that can ensure that resin composition layer is led with being formed with when by varnish curing The range of the bonding force of the substrate of body wiring, additionally, it is preferred that for the landfill (flowing that can ensure that the substrate for being formed with conductor wiring Property) range.
As brushing method (machine for brushing), using die coating machine, comma coating machine, bar coater, kiss painting machine, roll coater etc., Can be suitably subject to according to the thickness of the film containing resin using.As drying means, heating or blowing hot wind etc. can be used.
Drying condition is not particularly limited, usually so that the content of the organic solvent of resin composition layer becomes 10 mass % Hereinafter, being dried it is preferred that becoming 5 mass % modes below.The boiling point of the amount of organic solvent in varnish because of organic solvent It is different and different, still, such as by carrying out 3 to the varnish of the organic solvent containing 30~60 mass % at 50~150 DEG C Drying in~10 minutes or so, so as to form resin composition layer.For drying condition, preferably first pass through in advance simple Experiment is to set appropriate, preferred drying condition.
The thickness of the resin composition layer formed in the film containing resin is typically set to the thickness of conductor layer or more.Electricity The thickness of conductor layer possessed by base board is preferably 5~70 μm, more excellent in order to make printed wiring board become light and short It is selected as 3~50 μm, most preferably 5~30 μm.Thus, thickness of the thickness of resin composition layer preferably than such conductor layer is thick 5% or more.
Supporting mass film in the present invention can be enumerated by the polyolefin such as polyethylene, polypropylene, polyvinyl chloride, poly terephthalic acid Glycol ester (hereinafter sometimes referred to simply as " PET ".), the polyester such as polyethylene naphthalate, polycarbonate, the shapes such as polyimides At film；Processing release paper, copper foil, metal foils such as aluminium foil etc. can also be enumerated.
It should be noted that delustring processing, sided corona treatment can be implemented to supporting mass film and aftermentioned protective film, except this with Outside, demoulding processing can also be implemented.
The thickness of supporting mass film is not particularly limited, can also be at preferably 10~150 μm and more preferably 25~50 μm The not protective film opposite with supporting mass film with stacking on the face for supporting film closely sealed of resin composition layer.
The thickness of protective film is not particularly limited, and for example, 1~40 μm.It is different so as to prevent by the way that protective film is laminated Object is mixed into.Film containing resin can also be wound in roll to store.
Printed wiring board (multilayer printed circuit of the invention is manufactured as the film of the invention containing resin is used Wiring plate) method mode, as long as such as the film layer containing resin to be pressed in the single side of circuit substrate using vacuum laminator Or it is two-sided upper.
As the substrate used in circuit substrate, for example, can enumerate glass epoxy substrate, metal substrate, polyester substrate, Polyimide substrate, BT resin substrate, thermohardening type polyphenylene oxide substrate etc..
It should be noted that here, circuit substrate, which refers to, is formed with conductor in the single or double of above-mentioned such substrate It is routed the substrate of (circuit).In addition, multilayer printed circuit cloth obtained by just conductor layer and resin composition layer are alternatively laminated For line plate, the outermost single or double of multilayer printed wiring board is formed with the wiring plate of conductor wiring (circuit) Included in circuit substrate mentioned here.Conductor wiring layer surface can be implemented at roughening in advance by blackening process etc. Reason.
In addition, forming coated metal foil in the case where at least one face of the film containing resin is formed with conductor layer Plywood.
For above-mentioned lamination, in the case where the film containing resin has protective film, after said protection film is removed, root The film containing resin and circuit substrate are preheated according to needs, while the film containing resin is pressurizeed and is heated, It is crimped on circuit substrate.In the present invention, it is preferred to be carried out under reduced pressure to circuit substrate using using vacuum layer platen press The method of lamination.
Lamination is not particularly limited, such as crimping temperature (laminating temperature) is preferably set as 70~140 DEG C, will crimp Pressure is set as 0.1~1.1MPa, is laminated in the case where air presses 20mmHg (26.7hPa) reduced pressure below.In addition, lamination Method can be also possible to the continous way using roller with batch-type.
After film layer containing resin is pressed on circuit substrate, be cooled to room temperature near, then will support film stripping when, can By being removed, heat cure, and resin composition layer is formed on circuit substrate.As long as the condition of heat cure is according to resin group Type, the content of resin component etc. closed in object are properly selected, and are preferably carried out 20 minutes at 150 DEG C~220 DEG C ~180 minutes, more preferably 160 DEG C~200 DEG C carry out 30~120 minutes in the range of selected.
After forming resin composition layer, in the case where will not supporting film stripping before being solidified, at this moment into Row removing.Then, as needed, aperture is carried out to the resin composition layer being formed on circuit substrate, forms via hole, leads to Hole.Aperture is for example carried out using method well known to drilling, laser, plasma etc., and combines the above method as needed It to carry out, but is most common method by means of the aperture of the laser such as carbon dioxide laser, YAG laser.
Conductor layer is formed next, being plated on resin composition layer by dry type plating or wet type.As dry type plating, The known methods such as vapor deposition, sputtering, ion plating can be used.In the case where wet type plating, firstly, utilizing permanganate (Gao Meng Sour potassium, sodium permanganate etc.), bichromate, ozone, hydrogen peroxide/sulfuric acid, the oxidants such as nitric acid are to cured resin combination The surface of layer is roughened, and forms the anchor of convex-concave.As oxidant, potassium permanganate, sodium permanganate are particularly preferably used Deng sodium hydrate aqueous solution (alkaline permanganic acid aqueous solution).Then, it is obtained using combining electroless plating with electrolytic coating Method formed conductor layer.In addition, can also form the plating protective layer with conductor layer opposite pattern, and merely with electroless plating Form conductor layer.As the method for formation conductor wiring thereafter, for example, well known metal covering etch, half can be used to add Method etc..
Prepreg of the invention is to be immersed in the piece being made of fiber by containing varnish of the invention using solvent method etc. It in shape enhancing base materials, is then heated, to carry out B-stage and manufacture.That is, can be made into is impregnated with varnish of the invention Prepreg obtained by the flake reinforcement substrate being made of fiber.
As the flake reinforcement substrate being made of fiber, such as it may be used in various electrically insulating material plywoods and is made Known substrate.As the example of its material, the inorganic matter fibers such as E glass, D glass, S glass and Q glass can be enumerated, The organic fibers such as polyimides, polyester and polytetrafluoroethylene (PTFE) and their mixture etc..
For these substrates for example with shapes such as woven fabric, non-woven fabrics, slubbing yarn, chopped mat and surface felts, material and shape can It is selected according to the purposes of target molding, performance, as needed, may be used alone or in combination material and shape of more than two kinds Shape.The thickness of substrate is not particularly limited, for example, can be used about 0.03~0.5mm thickness, and from heat resistance, moisture-proof, plus It sets out in terms of work, preferably implement the substrate of surface treatment using silane coupling agent etc. or mechanically implements at fibrillation The substrate of reason.
Solvent method is to be immersed in flake reinforcement substrate in varnish of the invention and contain varnish and be immersed in flake reinforcement substrate In, the method that is then dried.
Next, the method for manufacturing multilayer printed wiring board as prepreg obtained as described above is used, Such as make 1 piece or make several pieces of prepregs of the invention Chong Die with circuit substrate as needed, metal is utilized across mold release film Plate clamping, carries out extruding stacking under that condition of pressurizing and heat.The preferred pressure of pressurized, heated condition is 0.5~4Mpa, temperature It is 120~200 DEG C, 20~100 minutes.In addition, identical as the film containing resin, also using vacuum layer platen press by prepreg It is laminated on circuit substrate, is then heating and curing.Then, identical operation can be carried out with above-mentioned documented method, it will After cured prepreg surface roughening, conductor layer is formed by plating, to manufacture multilayer printed wiring board.
Embodiment
Hereinafter, based on embodiment, the present invention is described in detail, but the present invention is not limited thereto.
Embodiment 1
Dihydro anthracene type epoxy resin (quotient is put into four mouthfuls of removable flasks for having thermometer, cooling tube, agitating device The name of an article: YX-8800, Japanese epoxy resin Co. Ltd. system epoxide equivalent: 174~183) 200g, as the chemical combination with amino Benzoguanamine (Japanese catalyst Co. Ltd. system) 13.8g of object, as the compound with phenolic hydroxyl group cresol novolac it is clear Coating resins (trade name: KA-1165, Dainippon Ink. & Chemicals Inc's system, hydroxyl equivalent: 119) 13.2g, as molten Propylene glycol methyl ether acetate (Kanto Kagaku K. K.'s system) 170.2g of agent, carries out heating stirring at 140 DEG C.Confirming After material has dissolved, further heating 10 minutes, then take out varnish 1g, use high performance liquid chromatography (chromatographic column: Tosoh Co. Ltd. system TSK-gel G-3000H), the weight average molecular weight before finding out the reaction of polystyrene conversion.It is being maintained at 140 It in the state of DEG C, reacts 5 hours, then takes out varnish 1g, the weight for finding out polystyrene conversion using high performance liquid chromatography is equal Molecular weight.Then, cresol novolac resin (KA-1165, Dainippon Ink. & Chemicals Inc's system, commodity is added Name) 92.0g, 30 minutes heating for dissolving are carried out at 100 DEG C, to make varnish.
Varnish 1ml obtained by production is taken out, after the particle that confirmed 5 μm of no partial size or more using hondrometer, at 5 DEG C It is taken care of, by estimating the time that confirmed that material is precipitated from varnish.In the case where confirmed that material is precipitated, take out clear 1ml is painted, using hondrometer measurement whether there is or not 5 μm of partial size or more of particle, until finding out the particle until that can confirm 5 μm or more Time is as the storage time.
Embodiment 2
Benzoguanamine (Japanese catalyst Co. Ltd. system) is set as 27.6g, by cresol novolac resin (KA- 1165, Dainippon Ink. & Chemicals Inc's system, trade name) it is set as 22.6g, by the propylene glycol methyl ether acetate (Northeast Chemical Co., Ltd. system) it is set as 162.8g, by the cresol novolac resin added after the reaction (KA-1165, big Japan Ink chemistry Industrial Co., Ltd system, trade name) it is set as 56.3g, in addition to this, operation same as Example 1 is carried out, made Varnish finds out the storage time.
Embodiment 3
It will be set as 4.6g as the melamine of the compound with amino (Kanto Kagaku K. K.'s system), it will be as tool There is the cresol novolac resin (trade name: KA-1165, big Japanese ink chemical industry strain formula meeting of the compound of phenolic hydroxyl group Society's system) it is set as 26.2g, propylene glycol methyl ether acetate (Kanto Kagaku K. K.'s system) is set as 172.2g, by institute after reaction Additional cresol novolac resin (KA-1165, Dainippon Ink. & Chemicals Inc's system, trade name) is set as 46.0g carries out operation same as Example 1 in addition to this, makes varnish, finds out the storage time.
Embodiment 4
By as the dicyandiamide of the compound with amino (Kanto Kagaku K. K.'s system) be set as 11.6g, will be used as it is molten The cresol novolac that the propylene glycol methyl ether acetate (Kanto Kagaku K. K.'s system) of agent is set as 118.8g, will be added after reaction Varnish gum (KA-1165, Dainippon Ink. & Chemicals Inc's system, trade name) is set as 65.8g, by 140 DEG C of reaction Time is set as 3 hours, in addition to this, carries out operation same as Example 1, makes varnish, find out the storage time.
Embodiment 5
Dicyandiamide (Kanto Kagaku K. K.'s system) is set as 2.4g, by cresol novolac resin (trade name: KA- 1165, Dainippon Ink. & Chemicals Inc's system) it is set as 26.2g, by propylene glycol methyl ether acetate (Northeast chemistry strain formula Commercial firm's system) it is set as 137.4g, by the cresol novolac resin added after reaction (KA-1165, big Japanese ink chemistry work Industry Co. Ltd. system, trade name) it is set as 46.0g, in addition to this, operation same as Example 1 is carried out, makes varnish, find out Storage time.
Embodiment 6
By as the naphthol novolak type epoxy resin of epoxy resin, (trade name: ESN-175, Dongdu are melted into epoxy processed and work as Amount: 254) it is set as 200g, dicyandiamide (Kanto Kagaku K. K.'s system) is set as 3.3g, will be as the chemical combination with phenolic hydroxyl group Object phenol resol resins (trade name: TD-2090, Dainippon Ink. & Chemicals Inc's system, hydroxyl equivalent: 105) it is set as 24.8g, propylene glycol methyl ether acetate (Kanto Kagaku K. K.'s system) is set as 115.5g, will be chased after after reaction The phenol resol resins (TD-2090, Dainippon Ink. & Chemicals Inc's system, trade name) added be set as 41.3g, 140 DEG C of storage time is set as 3 hours, in addition to this, operation same as Example 1 is carried out, makes varnish, find out keeping Time.
Embodiment 7
By the biphenyl phenolic resin varnish type epoxy resin (commodity as epoxy resin other than dihydro anthracene type epoxy resin Name: NC-3000-H Nippon Kayaku K. K system, epoxide equivalent: 284~294) it is set as 76.8g, will be as with amino The amino triazine novolac resin (trade name: LA3018-50P, Dainippon Ink Chemicals's system, 50% solution) of compound is set as 62.6g, will be as the cresol novolac resin of the compound with phenolic hydroxyl group (trade name: KA-1165, big Japanese ink Chemical industry Co. Ltd. system) it is set as 14.8g, is set as propylene glycol methyl ether acetate (Kanto Kagaku K. K.'s system) 230.5g, cresol novolac resin (KA-1165, Dainippon Ink. & Chemicals Inc that will be added after reaction System, trade name) be set as 124.9g, reaction temperature is set as 120 DEG C, 14 hours will be set as the retention time, in addition to this, carry out with The identical operation of embodiment 1 makes varnish, finds out the storage time.
Embodiment 8
By the biphenyl phenolic resin varnish type epoxy resin (commodity as epoxy resin other than dihydro anthracene type epoxy resin Name: NC-3000-H Nippon Kayaku K. K system, epoxide equivalent: 284~294) it is set as 76.8g, will be as with amino The dicyandiamide (Kanto Kagaku K. K.'s system) of compound is set as 3.8g, by the cresols phenol as the compound with phenolic hydroxyl group Novolac resin (trade name: KA-1165, Dainippon Ink. & Chemicals Inc's system) is set as 18.1g, by propylene glycol list The cresol novolac resin that methyl ether acetate (Kanto Kagaku K. K.'s system) is set as 113.0g, will be added after reaction (KA-1165, Dainippon Ink. & Chemicals Inc's system, trade name) is set as 124.9g, by propylene glycol methyl ether acetate (Kanto Kagaku K. K.'s system) is set as 115.1g, in addition to this, carries out operation same as Example 1, makes varnish, find out Storage time.
Embodiment 9
By the biphenyl phenolic resin varnish type epoxy resin (commodity as epoxy resin other than dihydro anthracene type epoxy resin Name: NC-3000-H Nippon Kayaku K. K system, epoxide equivalent: 284~294) it is set as 200.5g, will be as with amino The dicyandiamide (Kanto Kagaku K. K.'s system) of compound is set as 3.9g, by the cresols phenol as the compound with phenolic hydroxyl group Novolac resin (trade name: KA-1165, Dainippon Ink. & Chemicals Inc's system) is set as 197.2g, by propylene glycol list The propylene glycol methyl ether acetate that methyl ether acetate (Kanto Kagaku K. K.'s system) is set as 161.6g, will be added after reaction (Kanto Kagaku K. K.'s system) is set as 164.7g, in addition to this, carries out operation same as Example 1, makes varnish.It carries out It makes and finds out the storage time.
Comparative example 1
Dihydro anthracene type epoxy resin (quotient is put into four mouthfuls of removable flasks for having thermometer, cooling tube, agitating device The name of an article: YX-8800, Japanese epoxy resin Co. Ltd. system) 200g, the benzoguanamine (Japan as the compound with amino Catalyst Co. Ltd. system) 13.8g, as the compound with phenolic hydroxyl group cresol novolac resin it is (KA-1165, big Japanese ink chemical industry Co. Ltd. system, trade name) 105.2g, the propylene glycol methyl ether acetate (Northeast as solvent Learn Co. Ltd. system) 170.2g, it is dissolved by heating at 140 DEG C, makes varnish.
It takes out production and obtains varnish 1ml, after the particle that confirmed 5 μm of no partial size or more using hondrometer, protect at 5 DEG C Pipe, by estimating the time that confirmed that material is precipitated from varnish.In the case where confirmed that material is precipitated, varnish 1ml is taken out, It is investigated using hondrometer and finds out the time until the particle that can confirm 5 μm or more whether there is or not 5 μm of partial size or more of particle as guarantor The pipe time.
Comparative example 2
Benzoguanamine (Japanese catalyst Co. Ltd. system) is set as 27.6g, by cresol novolac resin (KA- 1165, Dainippon Ink. & Chemicals Inc's system, trade name) it is set as 78.9g, by the propylene glycol methyl ether acetate (Northeast Chemical Co., Ltd. system) it is set as 162.8g, in addition to this, operation identical with comparative example 1 is carried out, makes varnish, find out keeping Time.
Comparative example 3
4.6g will be set as, by cresols phenol as the melamine of the compound with amino (Kanto Kagaku K. K.'s system) Novolac resin (KA-1165, Dainippon Ink. & Chemicals Inc's system, trade name) is set as 72.2g, by propylene glycol list Methyl ether acetate (Kanto Kagaku K. K.'s system) is set as 172.2g, in addition to this, carries out operation identical with comparative example 1, system Make varnish, finds out the storage time.
Comparative example 4
Dicyandiamide (Kanto Kagaku K. K.'s system) is set as 11.6g, cresol novolac resin is (KA-1165, big Japanese ink chemical industry Co. Ltd. system trade name) it is set as 65.8g, (will be closed as the propylene glycol methyl ether acetate of solvent Eastern Chemical Co., Ltd. system) it is set as 118.8g, in addition to this, operation identical with comparative example 1 is carried out, makes varnish, find out guarantor The pipe time.
Comparative example 5
2.4g will be set as, by cresol novolac as the dicyandiamide of the compound with amino (Kanto Kagaku K. K.'s system) Varnish gum (KA-1165, Dainippon Ink. & Chemicals Inc's system, trade name) is set as 72.2g, by propylene glycol list first Ether acetic acid ester (Kanto Kagaku K. K.'s system) is set as 137.4g, in addition to this, carries out operation identical with comparative example 1, production Varnish finds out the storage time.
Comparative example 6
It will be set as the naphthol novolak type epoxy resin of epoxy resin (ESN-175, Dongdu chemical conversion system, trade name) 200g, it will be set as 3.3g as the dicyandiamide of the compound with amino (Kanto Kagaku K. K.'s system), will be used as with phenol Phenol resol resins (TD-2090, Dainippon Ink. & Chemicals Inc's system, commodity of the compound of property hydroxyl Name) it is set as 65.0g, propylene glycol methyl ether acetate (Kanto Kagaku K. K.'s system) is set as 115.5g, in addition to this, carry out Operation identical with comparative example 1 makes varnish, finds out the storage time.
Comparative example 7
By the biphenyl phenolic resin varnish type epoxy resin (commodity as epoxy resin other than dihydro anthracene type epoxy resin Name: NC-3000-H Nippon Kayaku K. K system, epoxide equivalent: 284~294) it is set as 76.8g, will be as the change with amino The amino triazine novolac resin (trade name: LA3018-50P, Dainippon Ink Chemicals's system, 50% solution) for closing object is set as 62.6g, will be as the cresol novolac resin of the compound with phenolic hydroxyl group (trade name: KA-1165, big Japanese ink Chemical industry Co. Ltd. system) it is set as 139.7g, is set as propylene glycol methyl ether acetate (Kanto Kagaku K. K.'s system) 230.5g carries out operation identical with comparative example 1 in addition to this, makes varnish, finds out the storage time.
Comparative example 8
By the biphenyl phenolic resin varnish type epoxy resin (commodity as epoxy resin other than dihydro anthracene type epoxy resin Name: NC-3000-H Nippon Kayaku K. K system, epoxide equivalent: 284~294) it is set as 76.8g, will be as the change with amino The dicyandiamide (Kanto Kagaku K. K.'s system) for closing object is set as 3.8g, by the cresol novolac as the compound with phenolic hydroxyl group Varnish gum (trade name: KA-1165, Dainippon Ink. & Chemicals Inc's system) is set as 143.0g, by propylene glycol list first Ether acetic acid ester (Kanto Kagaku K. K.'s system) is set as 228.1g, in addition to this, carries out operation identical with comparative example 1, production Varnish finds out the storage time.
Comparative example 9
By the biphenyl phenolic resin varnish type epoxy resin (commodity as epoxy resin other than dihydro anthracene type epoxy resin Name: it NC-3000-H Nippon Kayaku K. K system, epoxide equivalent: 284~294) is set as 200.5g, will be used as with amino The dicyandiamide (Kanto Kagaku K. K.'s system) of compound be set as 3.9g, by the cresols phenol as the chemical combination with phenolic hydroxyl group Novolac resin (trade name: KA-1165, Dainippon Ink. & Chemicals Inc's system) is set as 197.2g, by propylene glycol list Methyl ether acetate (Kanto Kagaku K. K.'s system) is set as 326.3g, in addition to this, carries out operation identical with comparative example 1, system Make varnish.It is made and finds out the storage time.
The weight average molecular weight of varnish obtained by making in embodiment is shown with storage time measurement result by the following table 1.Separately Outside, the storage time measurement result of varnish obtained by making in a comparative example is shown by the following table 2.
[table 1]
[table 2]
The storage time of the Examples 1 to 6 of table 1 is 168 hours or more, i.e., with 1 week or more storage time, with this phase Right, the storage time of the comparative example 1~6 of table 2 is shorter, is 2~5 hours.Contain polycycle shown by embodiment and comparative example The epoxy resin of structure is referred to as Cristalline epoxy resin.Dissolubility relative to solvent is low.Therefore, even if by the temperature of varnish The fusing point that degree is increased to epoxy resin is melted, and in the case where returning again to room temperature, can also start to be precipitated in a short time.With This is opposite, in Examples 1 to 6, by reacting the functional group of a part of epoxy resin, thus even if at 5 DEG C Also it can reach 30 times or more of the storage time of comparative example under maintaining requirement.Thus, it is known that make the epoxy containing polycycle structure It is critically important that a part of functional group of resin, which is reacted in terms of ensuring the storage time,.Moreover, the varnish of the present embodiment with It is previous different, it can be improved dissolubility, realize the stabilisation of varnish, realize the long-term preservation of varnish, be that operability is excellent therefore And the varnish that storage stability is high.
In addition, the coefficient of thermal expansion for the plywood for being coated copper obtained by making using the varnish of embodiment is also low, it is therefore contemplated that Even if being also able to suppress the generation of the previous warpage as problem in the case where printed wiring board is made.
Symbol description
10: semiconductor chip
12: sealing material (semiconductor packages)
14: bonding wire
16: conductor package substrate
18: substrate
20: through-hole
22: soldered ball
C: the crack generated by warpage

Claims (15)

1. a kind of varnish, which is characterized in that it is made in a solvent containing selected from biphenyl structural, biphenyl novolac resin knot The polycycle structure of at least one of structure, naphthol novolak varnish gum structure, anthracene structure and dihydroanthracene structure and have at least one A part of the epoxy group of the resin of a epoxy group is reacted with the amino of the compound with amino and is made ,
The resin component for the structure that the varnish contains the structure indicated with following formula (1) and following formula (2) indicates, in resin component Relative to the formula (1) indicate structure and the formula (2) indicate structure the respective summation there are ratio for, institute State formula (1) expression structure there are ratio be 40% hereinafter,
In the formula (1), R1For the residue of the compound with amino,
2. a kind of varnish, which is characterized in that it is made in a solvent containing selected from biphenyl structural, biphenyl novolac resin knot The polycycle structure of at least one of structure, naphthol novolak varnish gum structure, anthracene structure and dihydroanthracene structure and have at least one The amino of a part of the epoxy group of the resin of a epoxy group and the compound with amino and with phenolic hydroxyl group Prepared by the phenolic hydroxyl group of compound is reacted,
The varnish contains the structure of the structure, the structure that following formula (2) indicates and following formula (10) expression that indicate with following formula (1) Resin component, the structure and the formula that the structure indicated relative to the formula (1), the formula (2) in resin component indicate (10) for the summation there are ratio of the structure indicated, the structure for structure and the formula (10) expression that the formula (1) indicates There are ratio add up to 40% hereinafter,
In the formula (1), R1For the residue of the compound with amino,
3. varnish according to claim 1 or 2, wherein the compound with amino is guanamines, dicyandiamide and amino Any compound in triazine novolac resin.
4. a kind of prepreg, which is characterized in that be that varnish of any of claims 1 or 2 is coated on substrate, and heats dry Prepared by dry.
5. prepreg according to claim 4, wherein the substrate is glass woven fabric, glass non-woven fabric, aromatics polyamides Amine woven fabric or aramid nonwoven fabric.
6. a kind of film of resin layer, which is characterized in that be that varnish of any of claims 1 or 2 is coated on film, and heats Prepared by drying.
7. a kind of plywood of coated metal foil, which is characterized in that at least one face of prepreg as claimed in claim 4 With conductor layer.
8. a kind of plywood of coated metal foil, which is characterized in that at least the one of the film of resin layer as claimed in claim 6 A face has conductor layer.
9. a kind of printed wiring board, which is characterized in that be the stacking to the coated metal foil described in claim 7 or 8 Prepared by the formation that the conductor layer possessed by least one face of plate is routed.
10. application of the varnish of any of claims 1 or 2 in manufacture prepreg, wherein will be of any of claims 1 or 2 Varnish is coated on substrate, is thermally dried and forms prepreg.
11. the application in 0 according to claim 1, wherein the substrate is that glass woven fabric, glass non-woven fabric, aromatic polyamides are knitted Cloth or aramid nonwoven fabric.
12. application of the varnish of any of claims 1 or 2 in film of the manufacture containing resin, wherein by claims 1 or 2 institute The varnish stated is coated on film, and heat drying and be made with resin layer film.
13. application of the prepreg as claimed in claim 4 in the plywood of manufacture coated metal foil, in claim 4 institute At least one face for the prepreg stated is equipped with conductor layer.
14. application of the film as claimed in claim 6 containing resin in the plywood of manufacture coated metal foil, in claim At least one face of film described in 6 containing resin is equipped with conductor layer.
15. application of the plywood of coated metal foil described in claim 7 or 8 in manufacture printed wiring board, in right It is required that the formation that the conductor layer possessed by least one face of the plywood of coated metal foil described in 7 or 8 is routed And printed wiring board is made.
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